JPH0397715A - Production of modified polyol and polyurethane - Google Patents

Abstract

PURPOSE:To obtain a low-viscosity modified polyol good in flameretardancy, high frequency fusibility and dispersibility, useful as a raw material for polyurethanes by polymerization of monomer component containing vinyl chloride, etc., in polyether polyol in the presence of an initiator having specific solubility. CONSTITUTION:The objective modified polyol can be obtained by polymerization in polyether polyol of (A) an ethylenic unsaturated monomer component containing >=5wt.% of vinyl chloride and/or vinylidene chloride using (B) as part or the whole of initiator, an initiator with a solubility of >=0.5 pts.wt. per 100 pts.wt. of the polyether polyol [e.g. 2,2'azobis(2-methybutylonitrile)]. The present modified polyol, as at least part of active hydrogen atom-contg. compound, is reacted with a polyisocyanate, if needed, in the presence of catalyst. foaming agent and/or additive(s), to obtain the other objective polyurethane.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a modified polyol and a method for producing polyurethane using the same.

[Prior Art] Conventionally, as a method for producing modified polyols, a method is known in which an ethylenically unsaturated monomer such as vinyl chloride is polymerized using a peroxide radical forming agent or the like in a polyether polyol.

[Problems to be Solved by the Invention] However, in this method for producing modified polyols, when attempting to obtain sufficient flame retardancy and high frequency fusion properties, the dispersibility of the modified polyol becomes poor and the viscosity becomes high. There is a point.

[Means for Solving the Problems] The present inventors have studied a method for producing a modified polyol that has sufficient flame retardancy and high-frequency fusion properties, good dispersibility, and low viscosity, and a method for producing polyurethane using the same. As a result of repeated efforts, we have arrived at the present invention.

That is, the present invention provides a method for producing a modified polyol in which an ethylenically unsaturated monomer (11) is polymerized in a polyether polyol (i) in the presence of an initiator (111), in which at least one of the monomers (11) is polymerized. 5% by weight consists of vinyl chloride and/or vinylidene chloride, and the initiator (iii
) as at least a part of the polyether polyol (
i) A modified polyol (a) characterized by using an initiator having a solubility of 0.5 part or more per 100 parts by weight.
Production method: A method for producing polyurethane by reacting a polyisocyanate and an active hydrogen atom-containing compound in the presence of a catalyst, a blowing agent, and other additives if necessary, as at least a part of the active hydrogen atom-containing compound. , a method for producing a polyurethane characterized by using the modified polyol (a) according to any one of claims 1 to 6; and a polyisocyanate and an active hydrogen atom-containing compound, if necessary, in the presence of a catalyst, a leachant, and other additives. A method for producing polyurethane foam by reacting in the presence of an additive,
A method for producing a polyurethane foam, characterized in that the modified polyol (a) according to any one of claims 1 to 7 is used as at least a part of the active hydrogen atom-containing compound.

In the present invention, the initiator (iii) is room temperature (2
5° C.), the solubility in the polyether polyol (i) is usually 0.5 parts or more per 100 parts by weight of the polyol,
Preferably it is 1 part or more, more preferably 2 parts or more. This solubility is. If it is less than 0.5 part, the polymerization rate will not increase.

In the present invention, the initiator (iii) is room temperature (2
59C), the solubility in vinyl chloride and/or vinylidene chloride is usually 1 part or more, preferably 2 parts or more, per 100 parts by weight of vinyl chloride or vinylidene chloride;
More preferably, the amount is 3 parts or more. If this solubility is less than 1 part, the polymerization rate will not increase.

In the present invention, as the initiator (iii), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), (1-phenylethyl ) azodiphenylmethane, dimethyl-2,2'-azobisisobutyrate,
2,2'-azobis(2-methylbutyronitrile), 1
, 1'-azobis(1-cyclohexanecarbonitrile), 2-(carbamoylazo)isobutyronitrile,
2,2'-azobis(2,4.4-}limethylpentane), 2-phenylazo 2,4-dimethyl-4-methoxyvalenitrile, 2,2'-azobis(2-methylbroban), 2.2 '-azobis(N,N'-dimethyleneisobutyramicin) dihydrochloride, 2,2'-azobis(2-amidinobroban) dihydrochloride, 2,2'-azobis(N,.N'-dimethylene) Examples include isobutyramidine L4,4'-azobis(4-cyanopentanoic acid) and mixtures of two or more thereof.

Among these, 2,2”-azobis(2,4
-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate and 2,2'-azobis(2-
methylbutyronitrile). The effects of the present invention cannot be obtained with an azo initiator, such as azobisisobutyronitrile (AIBN), in which the solubility of the initiator is less than 0.5 parts.

In the present invention, the amount of salt {1-vinyl and/or vinylidene chloride in monomer (ii) is usually 5 to 100% by weight, preferably 30 to 100% by weight of monomer (ii).
, more preferably 50 to 100% by weight. The amount of vinyl chloride and/or vinylidene chloride in the monomer is 5
If the weight percent is ungrooved, sufficient flame retardancy and high frequency weldability cannot be obtained.

In the present invention, aromatic hydrocarbon monomers, unsaturated nitrites, and (meth)acrylic acid esters are used as ethylene monomers other than vinyl chloride and/or vinylidene chloride in the total monomers. It can be used in a range of 0 to 95% by weight.

Examples of aromatic hydrocarbon monomers include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, and chloromethylstyrene.

Examples of unsaturated nitriles include (meth)acrylic nitriles.

(Meth)acrylic acid esters include (meth)acrylic acid alkyl esters (alkyl group has 1 to 30 carbon atoms).
) etc. Specifically, methyl (meth)acrylate, butyl (meth)acrylate, nonyl (meth)acrylate,
Decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, eicosyl ( meth)acrylate, docosyl(
Examples include meta)acrylate.

In addition to the above, other monomers may be used if necessary. These monomers include ethylenically unsaturated carboxylic acids and their derivatives [(meth)acrylic acid, (meth)acrylamide, etc.], aliphatic hydrocarbon monomers [ethylene,
brobylene, etc.], halogen-containing vinyl monomers [perfluorooctylethyl methacrylate, perfluorooctylethyl acrylate, allyl chloride, methallyl chloride, etc.], nitrogen-containing vinyl monomers [diaminoethyl methacrylate, morpholinoethyl methacrylate, etc.], both Examples include vinyl-terminated silicone.

In the present invention, the amount of the ethylenically unsaturated monomer (11) used in the production of the modified polyol (a) is 100 parts (
The amount is usually 1 to 80 parts, preferably 5 to 60 parts per part by weight. If the amount of monomer (ii) exceeds 80 parts, the polyether layer and the polymer layer will separate, and the viscosity will increase significantly. If it is less than 1 part, flame retardancy and high frequency welding properties are not achieved.

In the present invention, the polyether polyol (i) used in the production of the modified polyol (a) is a compound having at least 2 (preferably 2 to 8) active hydrogen atoms (for example, polyhydric alcohol, polyhydric phenol, amine Examples include compounds with a structure in which alkylene oxide is added to (eg, polycarboxylic acids, phosphoric acids, etc.) and mixtures thereof.

Examples of the polyhydric alcohols include alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexasidiol, and neopentyl glycol, and diols having a cyclic group ( For example, dihydric alcohols such as those described in Japanese Patent Publication No. 45-1474); trihydric alcohols such as glycerin, trimethylolbroban, trimethylolethane, hexanetriol, triethanolamine; bentaerythritol, methyl glycoside, Tetrahydric alcohols such as glycerin; and sugar alcohols with higher functional groups such as pentitol such as adonitol, arabitol, xylitol, hexitols such as sorbitol, mannitol, iditol, talitol, dulcitol; sugars such as glucose, mannose, fructose, sorbose Monosaccharides such as sucrose, oligosaccharides such as sucrose, crehalose, lactose, raffinose; glycosides such as glycosides of polyols (e.g. glycols such as ethylene glycol, brobylene glycol, alkane polyols such as glycerin, trimethylolpropane, hexanetriol); Bori (alkane polyol)
For example, polyglycerols such as triglycerin and tetraglycerin. Examples include polybentaerythritol such as dipentaerythritol and tripentaerythritol; and cycloalkane polyols such as tetrakis(hydroxymethyl)cyclohexanol.

The above-mentioned polyhydric phenols include monocyclic polyhydric phenols such as birogallol, hydroquinone, and phloroglucin; bisphenols such as bisphenol A and bisphenol sulfone; metal condensates of phenol and formaldehyde (
(novolac), for example, borifphenol described in US Pat. No. 3,265,641.

Examples of amines include ammonia; mono-, di-, and I-alkanolamines such as ethanolamine, isobrobanolamine, and aminoethylethanolamine; C, to C23 alkylamines; C2 to C6 alkylene diamines, such as ethylene diamine, propylene diamine; , hexamethylene diamine, polyalkylene polyamines such as diethylene triamine, triethylene tetramine, and other aliphatic amines: aniline, phenylene diamine, diaminotoluene, xylylene diamine, methylene dianiline, diphenyl ether diamine, and the above (ii). Other aromatic amines listed as examples; alicyclic amines such as isophorone diamine, cyclohexylene diamine, dicyclohexylmethane diamine; aminoethylpiverazine and other
Heterocyclic amines described in JP-A-21044 can be mentioned. Two or more of these active hydrogen atom-containing compounds may be used in combination. Among these, polyhydric alcohols are preferred.

Examples of the alkylene oxide to be added to the active hydrogen atom-containing compound include ethylene oxide (hereinafter abbreviated as E○), propylene oxide (hereinafter abbreviated as P○),
Examples include 1.2-, 1,3-, 1,4-, 2,3-butylene oxide, styrene oxide, and combinations of two or more of these (block and/or random addition).

Among the polyether polyols (i), those having a polyoxybrobylene chain and those having a polyoxybrobylene chain and a polyoxyethylene chain (ethylene oxide content of 25% by weight or less) are preferred.

The above-mentioned polyether polyols include those obtained by adding brobylene oxide (hereinafter abbreviated as P○) to the above-mentioned active hydrogen atom-containing compound, and P○ and other alkylene oxides (hereinafter abbreviated as A○), (1) PO- Added in the order of A○ (Chitubdo), (2) P〇1A〇1P〇1A
Those added in the order of ○ (balanced), (3) those added in the order of A〇1P○-AO, (4) those added in the order of P○-A〇1PO (active secondary), etc. Block adducts such as; (5) Random adducts obtained by mixing and adding PO and A○; and (6) JP-A-57-2
(7) Random/block additives such as those added in the order described in JP-A No. 09920 and (7) added in the order described in JP-A-53-13700. These may be used in combination.

The hydroxyl value (average) of the polyether polyol (i) is
Usually 15-100, preferably 20-70. 10
If it exceeds 0, the resulting modified polyol will have poor dispersibility.

The molecular weight of polyether polyol (i) is usually 2000
~30000 or more, preferably 2500-1
It is 0000. If the molecular weight is less than 2000, the resulting modified polyol will have poor dispersibility. When it exceeds 30,000, the viscosity of the obtained modified polyether increases.

In the present invention, the polymerization reaction can be carried out without a solvent, but it can also be carried out in the presence of an organic solvent (especially when the polymer concentration is high). Examples of organic solvents include benzene, toluene, xylene, acetonitrile, ethyl acetate, hexane, hebutane, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, isobrobyl alcohol, and n-butanol.

If necessary, chain transfer agents such as alkylmercaptanes (dodecylmerbutane, mercaptoethanol, etc.), alcohols (isobrobyl alcohol, methanol, 2-butanol, allyl alcohol, etc.),
Polymerization can be carried out in the presence of halogenated hydrocarbons (carbon tetrachloride, carbon tetrabromide, chloroform, etc.), enol ethers described in JP-A-55-31880, and the like.

Polymerization can be carried out either batchwise or continuously. The polymerization reaction is carried out at a temperature higher than the decomposition temperature of the polymerization initiator, usually 30 to 150°C, preferably 40 to 110°C, particularly preferably 50 to 110°C.
It can be carried out at 90°C, and it can also be carried out under atmospheric pressure, increased pressure, or even reduced pressure.

After the polymerization reaction is complete, the resulting modified polyol can be used as is without any post-treatment; however, after the reaction is complete, impurities such as organic solvents, decomposition products of the polymerization initiator, and unreacted monomers should be removed by conventional means. desirable.

The hydroxyl value of the modified polyol (a) is usually 5 to 100, preferably 7 to 80, and more preferably 10 to 60.

In the polyurethane manufacturing method of the present invention, the modified polyol (a) can be used in combination with other active hydrogen atom-containing compounds if necessary. In addition to (a), other active hydrogen atom-containing compounds that may be used as necessary include high-molecular polyols (b), which are commonly used in polyurethane production.
) and/or a low-molecular active hydrogen atom-containing compound (c)
can be used.

Other polymer polyols that may be used in combination include:
Polyether polyols, polyester polyols, and polymer polyols can be used. Examples of the polyether polyol include those mentioned above as the raw material polyether polyol (i) in (a).

Polyester polyols include polyhydric alcohols (dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neobentyl glycol, or this and glycerin). , mixtures with trihydric or higher alcohols such as trimethylolbroban), polycarboxylic acids or their anhydrides, and ester-forming derivatives such as lower esters (e.g. adipic acid, sebacic acid, 2K maleic anhydride, phthalic anhydride). Acids, dimethyl terephthalate, etc.), or their anhydrides, and alkyleonoxides (E○, PO, etc.) are reacted (condensed), or lactones (epsilon-cabrolactone, etc.) are obtained by ring-opening polymerization. can be given.

As the polymer polyol, these polyols, polyether polyols and/or polyester polyols, etc.) and ethylenically unsaturated monomers [those mentioned as raw materials (11) in (a) above: acrylonitrile, styrene, etc.] are polymerized. Polyols obtained by
(published in the official bulletin) can be cited.

In addition, polybutadiene polyol, hydroxyl group-containing vinyl polymer (acrylic polyol) such as JP-A-58-5
Natural oil-based polyols such as those described in No. 7413 and No. 57414, castor oil, and modified polyols can also be used.

These polyols usually have 2 to 8 hydroxyl groups and 200-
It has an OH equivalent of 4,000, preferably 3 to 8 nol (acid groups) and a ○H equivalent of 400 to 3,000.

Among these, preferred are polyether polyols.

Low-molecular active hydrogen atom-containing compounds (
C) at least 2 pieces (preferably 2 to 3 pieces,
In particular, it is preferable to use a compound having a molecular weight of 500 or less (preferably 60-400) and having 2 active hydrogen atoms (hydroxyl group, amino group, mercapto group, etc., preferably hydroxyl group), such as a low-molecular polyol or amino alcohol. can. Examples of low-molecular polyols include dihydric alcohols such as ethylene glycol, diethylene glycol, dipropylene glycol, dibrobylene glycol, l,4-butanediol, neopentyl glycol, and hexanediol; glycerin, trimethylolpropane, pentaerythritol, and dipropylene glycol; Trihydric or higher polyhydric alcohols such as glycerin, α-methylglucoside, sorbitol, xylitol, mannitol, dipentaerythritol, glucose, fructose, sucrose; low molecular weight (e.g. molecular weight 200-400) polyhydric alcohol A○ addition substances (polyethylene glycol, polybrobylene glycol, etc.): low-molecular-weight diols having a cyclic group (e.g., propylene oxide adduct of bisphenol A as described in Japanese Patent Publication No. 45-1474); tertiary or quaternary diols; nitrogen atom-containing low-molecular-weight polyols [for example, those described in JP-A-54-130699 (N-alkyl dialkanolamines such as N-methyldiethanolamine, N-butyldiethanolamine, etc., and quaternized products thereof); Examples include alkanolamines (triethanolamine, tribropanolamine, etc.); thiodiethylene glycol, etc. Examples of amino alcohols include mono- or di-alkanolamines (eg, monoethanolamine, diethanolamine, monopropanolamine, etc.). Preferred among these are low-molecular polyols (especially diols), specifically ethylene glycol, ■,4-butanediol, neopentyl glycol, 1,6-hexanediol, and mixtures of two or more of these. It is.

Modified polyol (in the entire active hydrogen atom-containing compound [(a) and optionally (b) and/or (C)]
The amount of a) is usually at least 5% by weight, preferably from 10 to 80% by weight. If (a) is less than 5% by weight, flame retardancy and high frequency welding properties are not achieved.

The amount of other polymeric polyol (b) is usually 0 to 95% by weight
, preferably 0 to 80% by weight. If (b) exceeds 95% by weight, flame retardancy, high frequency weldability and hardness will not be achieved.

The amount of the low-molecular active hydrogen-containing llm compound (c) is usually O~3
0% by weight, preferably 0 to 10% by weight.

When (c) exceeds 30% by weight, the exothermic temperature during the reaction becomes high and scorch occurs.

As the organic polyisocyanate used in the present invention, those conventionally used in the production of polyurethane can be used. Such polyisocyanates include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding the carbon in the NCO group) (for example, 2,4- and/or 2.
6- }Lylene diisocyanate (TDI), crude T
I) L 2,4'- and/or 4,4'-diphenylmethane diisocyanate (MDI), crude MDl [
Crude diaminophenylmethane {condensation product of formaldehyde and aromatic amine (aniline) or mixtures thereof: diaminodiphenylmethane and a small amount (e.g. 5 to 2
0% by weight) of a trifunctional or higher functional polyamine} phosgene 4P compound: polyaryl polyisocyanate (PAP
I) etc.] ; Aliphatic polyisocyanates having 2 to 18 carbon atoms (e.g. hexamethylene diisocyanate, lysine diisocyanate, etc.); Alicyclic polyisocyanates having 4 to 15 carbon atoms (e.g. isophorone diisocyanate, dicyclohexylmethane diisocyanate); 15 aromatic aliphatic polyisocyanates (for example, xylylene diisocyanate, etc.); and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, puret group, uretdione group, uretonimine group, isocyanurate group, oxazolidone group-containing modified products, etc.); and patent application filed in 1973
Examples include polyisocyanates other than those described in JP 9-199160; and mixtures of two or more thereof. Among these, commercially readily available polyisocyanates such as 2,4- and 2,6-TDI
, and mixtures of these isomers, crude TDI, 4,
4'- and 2,4'-MDI, mixtures of these isomers, PAPI, also called crude MDI, and urethane groups, carbodiimide groups, allophanate groups, urea groups, puret groups derived from these polyisocyanates. , modified polyisocyanates containing isocyanurate groups.

In the present invention, the isocyanate index [NCO/equivalent stop of active hydrogen atom-containing group *
100] is usually 80 to 140, preferably 85 to 12
0, particularly preferably 95 to 115 {*total of active hydrogen-containing groups (hydroxyl group, amino group) other than carboxylic group}. Also, the isocyanate index is significantly higher than the above range (for example, 300 to i,ooo or higher).
It is also possible to incorporate polyisocyanurates into the polyurethane.

In the present invention, in order to accelerate the reaction, catalysts commonly used in polyurethane reactions [for example, amine catalysts (tertiary amines such as triethylene amine and N-ethylmorpholine), tin catalysts (stannous octylate, dibutyl Other metal catalysts (such as lead octylate) can be used. The amount of catalyst may be, for example, from about 0.001 to about 5%, based on the weight of the reaction mixture.
used.

Further, in the present invention, a blowing agent (for example, methylene chloride, monofluorotoric methane, water, etc.) can be used if necessary during the production of polyurethane. The amount of blowing agent used can vary depending on the desired density of the polyurethane.

A tonifying agent can be used as at least a part of other additives that can be used as necessary in the present invention. Examples of foam stabilizers include silicone surfactants (polysiloxane-polyoxyalkylene copolymers).

Other additives that can be used in the present invention include flame retardants, reaction retardants, coloring agents, internal desintegrators, antiaging agents, anti-destructive agents, plasticizers, bactericidal agents, carbon black, and other fillers. Known additives may be mentioned.

Polyurethane can be produced by a conventional method, and can be carried out by a known method such as a one-shot method, a semi-prebolymer method, or a pre-bolimer method. Manufacturing equipment commonly used can be used for producing polyurethane. In the case of no solvent, a device such as a seconder or an extruder can be used. Various types of unfoamed or foamed polyurethanes can be produced in closed or open molds. Polyurethane is usually produced by mixing and reacting raw materials using low or high pressure mechanical equipment.

Furthermore, polyurethane can also be produced by removing gas such as dissolved air in the raw materials or air mixed during mixing by a vacuum method before and after mixing the raw materials (especially before mixing the raw materials). The method of the present invention is useful in producing flexible molded foams and slab foams. Also R
Molding can also be carried out by IM (reaction injection molding) method.

[Examples] The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples. Note that parts and % represent parts by weight and % by weight, respectively.

The composition of the raw materials used in the Examples and Comparative Examples is as follows.

(1) Polyol B: Glycerin and sucrose (30/70
A polyol with a hydroxyl value of 42, to which P○ was added to (% by weight) and then E○ was added. The amount of E○ added was 10% by weight.

(2) Polyol A: A polyol with a hydroxyl value of 56, which is obtained by adding P○ to glycerin.

(3) Initiator A: bis(4-t-butylcyclohexyl) peroxydicarbonate (4) Initiator B: 2,2'-azobis(2,4-dimethylvaleronitrile) (5) Initiator C: 2 , 2'-azobis(2-methylbutyronitrile) Table 1 shows the solubility of initiators A, B, and C in polyol A, respectively.

Solubility was expressed as parts of initiator dissolved per part of polyol AIOO.

Table 1 (6) Polyisocyanate: TDI-80 (manufactured by Nippon Polyurethane Kogyo Co., Ltd.) (7) Catalyst: DABC○33LV (33% dibrobylene glycol solution of liethyndiamine) Neostane U-28 (tin catalyst ) [manufactured by Nitto Kasei Co., Ltd.] (8) Foam stabilizer: SRX-294A (polyether siloxane polymer) [manufactured by Toray Silicone Co., Ltd.] Example 1 About 240 parts of polyether polyol A and 82 parts of initiator. 4
portion was placed in an autoclave. This autoclave was maintained at about 700C, and about 60 parts of vinyl chloride was blown into it over about 2 hours. After completion of the blowing, the mixture was aged for about 1 hour, and then the remaining vinyl chloride was removed to obtain a modified polyol.

Example 2 The same procedure as in Example 1 was carried out except that initiator C was used instead of initiator B in Example 1.

Practical example 3 Approximately 400 parts of polyether polyol A and 7.2 parts of initiator B
portion was placed in an autoclave. This autoclave was maintained at about 70°C, and about 100 parts of vinyl chloride was blown into it over about 1 hour. After completion of the blowing, the mixture was aged for about 1 hour, and the remaining hibinyl salt was removed to obtain a modified polyol.

Comparative Example 1 Approximately 240 parts of polyether polyol A and 2.4 parts of initiator A
90 parts were placed in an autoclave, the autoclave was kept at about 70°C, and about 60 parts of vinyl chloride was blown into it over about 2 hours. After completion of the blowing, the mixture was aged for about 1 hour, and then the remaining vinyl chloride was removed to obtain a modified polyol.

Table 2 Example 4 About 240 parts of polyether polyol A, about 60 parts of vinylidene chloride, and 2.4 parts of initiator B were placed in an autoclave. The autoclave is kept at about 70°C and polymerized for about 2 hours. Thereafter, the mixture was aged for about 1 hour, and residual vinylidene chloride was removed to obtain a modified polyol.

Example 5 The same procedure as in Example 1 was carried out except that initiator C was used instead of initiator B in Example 1.

Example 6 About 400 parts of polyether polyol A, about 100 parts of vinylidene chloride, and 7.2 parts of initiator B were placed in an autoclave. This autoclave was kept at about 70°C and polymerized for about 1 hour. Thereafter, the mixture was aged for about 1 hour, and then the remaining vinylidene chloride was removed to obtain a modified polyol.

Comparative Example 2 About 240 parts of polyether polyol A, about 60 parts of vinylidene chloride, and 2.4 parts of initiator A were placed in an autoclave. The autoclave was kept at about 70°C and polymerized for about 2 hours. Thereafter, the mixture was aged for about 1 hour, and residual vinylidene chloride was removed to obtain a modified polyol.

Table 3 1 Modified polyol ■: Modified polyol produced in Example 1. Hydroxyl value: 3 4.3 Modified polyol ■: Modified polyol produced in Example 2. Hydroxyl value: 3 5.3 Modified polyol ■: Modified polyol produced in Example 3. Hydroxyl value: 3 5 2 Modified polyol ■: Modified polyol produced in Comparative Example 2. Hydroxyl value: 4 0 2 Modified polyol ■: Modified polyol produced in Example 4. Suishun group value: 3 4-9 Modified polyol ■: Modified polyol produced in Example 5. Hydroxyl value = 3 5.3 Modified polyol ■: Modified polyol produced in Example 6. Hydroxyl value: 3 5.7 Examples 7 to 12, Comparative Examples 3 and 4 Slab blasting was performed using the modified polyols produced in Example 16 and Comparative Examples 1 and 2 in Tables 2 and 3.

50 parts of modified polyol, 50 parts of polyol A (above),
SRX-294A1.5 part, DABC○33LV0.3
1 part, tolylene diisocyanate in a mixture of 4.5 parts water}
(TDI-80) was quickly mixed in an amount to give an NCO INDEX of 105, and a slab foam was foamed. The general physical properties of this foam are shown in Tables 4 and 5.

Further, Tables 6 and 7 show the results of flame retardancy and high frequency fusion properties of this foam.

The method for measuring flame retardancy is the flame retardant test method for automobile interior parts (F
MVSS302) was used for evaluation.

High frequency fusion properties were measured as follows. Prepare a nylon skin material, overlap the brushed surface of the nylon skin material on the anode blade side with the polyurethane foam backing material on the cathode plate side, and use a high frequency fusion machine (R-204 (18)
, Baal Kogyo Co., Ltd. under the conditions of a frequency of 40.46 MHz, a pressure of 5 kg/cn+2, a current of 0.2 A, and a bonding time of 5 seconds. ) to i. UI+ has been set.

Table-4 Table-5 Table-6 Table-7 The physical property measurement method is as follows.

Density (kg/m3): JISK6301 25%lL
D (kg/314cm2):. JIs K6382
Tensile strength (kg/cm2): J Is K6301
Tear strength (kg/cm): j Is K630
1 Cutting elongation (%): J ISK6301 Impact modulus (χ): J IsK6382 Compression set (
χ): JISK6382 [Effects of the Invention] Compared to conventional methods, the method for producing a modified polyol of the present invention can produce a modified polyol with sufficient flame retardancy and high-frequency fusion properties, good dispersibility, and low viscosity. I can do it.

Because of the above-mentioned effects, the polyurethane foam obtained by the present invention or the urethane manufacturing method uses a modified polyol that has better dispersibility and lower viscosity than conventional methods, and has sufficient flame retardancy and high frequency resistance. Because it has fusion properties, it is extremely useful for applications such as automobile interior parts and interior furnishings such as furniture.

Claims (1)

[Claims] 1. A method for producing a modified polyol in which an ethylenically unsaturated monomer (ii) is polymerized in a polyether polyol (i) in the presence of an initiator (iii), wherein the monomer ( ii
) consists of at least 5% by weight of vinyl chloride and/or vinylidene chloride, and has a solubility of 0.5 part or more per 100 parts by weight of the polyether polyol (i) as at least a part of the initiator (iii). A method for producing a modified polyol (a), characterized by using the following. 2. The initiator (iii) contains at least one of the monomers (
ii) vinyl chloride and/or vinylidene chloride in
2. The method according to claim 1, wherein said initiator has a solubility of 1 part per 00 parts by weight or more. 3. The monomer (ii) according to claim 1 or 2, wherein the monomer (ii) contains a monomer selected from the group consisting of aromatic hydrocarbon monomers, unsaturated nitriles, and (meth)acrylic acid esters. manufacturing method. 4. The amount of the monomer (ii) is 1 to 1 per 100 parts by weight of the polyether polyol (i) and the monomer (ii).
4. The method according to claim 1, wherein the amount is 80 parts by weight. 5. The polyether polyol (i) has a hydroxyl value of 15 to
100 polyether polyol. 6. The method according to any one of claims 1 to 5, wherein the polyether polyol (i) is a polyether polyol having two or more functional groups. 7. A method for producing polyurethane by reacting a polyisocyanate and an active hydrogen atom-containing compound in the presence of a catalyst, a blowing agent, and other additives if necessary, as at least a part of the active hydrogen atom-containing compound, A method for producing polyurethane, characterized in that the modified polyol (a) according to any one of claims 1 to 6 is used. 8. A method for producing polyurethane foam by reacting a polyisocyanate and an active hydrogen atom-containing compound in the presence of a catalyst, a blowing agent, and other additives if necessary, as at least a part of the active hydrogen atom-containing compound. , the modified polyol (a) according to any one of claims 1 to 7.
A method for manufacturing polyurethane foam characterized by using. 9. The manufacturing method according to claim 8, wherein a foam stabilizer is used as at least a part of the additive.